This application is an application under 35 U.S.C. Section 371 of International Application Number PCT/FR99/02933 filed on Nov. 26, 1999.
A subject-matter of the present invention is single-component organopolysiloxane compositions which are stable on storage in the absence of moisture and which crosslink to adherent and translucent elastomers in a thin layer (that is to say, within a thickness range in particular from 0.3 to 3 mm), the crosslinking being carried out from ambient temperature (that is to say, within a temperature range from 5xc2x0 C. to 35xc2x0 C.) and in the presence of moisture.
It is known to prepare compositions having these properties by blending mainly diorganopolysiloxane polymer(s) comprising end alkoxyl groups, inorganic filler(s) not generating opaqueness, silanes substituted by specific hydrolysable groups, agent(s) for improving adhesion and a curing (or crosslinking) catalyst.
Compositions of this type figure more especially in U.S. Pat. No. 5,674,936 and U.S. Pat. No. 5,698,653. The compositions in accordance with this prior art are formed by blending a diorganopolysiloxane polymer comprising end alkoxyl groups, a siliceous inorganic filler, a nonreactive diorganopolysiloxane polymer comprising end trialkylsiloxyl groups, a curing catalyst based on a tetraalkyl titanate and an agent for improving the adhesion consisting of a 1,3,5-tris(trialkoxysilyl)alkyl isocyanurate (in the case of U.S. Pat. No. 5,674,936) or of an epoxidized silane (in the case of U.S. Pat. No. 5,698,653).
The compositions in accordance with this prior art necessarily require the use, from the start, of an already functionalized diorganopolysiloxane polymer (comprising at least two alkoxyl groups at each chain end), which is obtained by reacting, in a separate preliminary stage, a tri- or a tetraalkoxysilane with a diorganopolysiloxane polymer comprising a hydroxyl group at each chain end in the presence of a catalyst. The compositions in accordance with this prior art necessarily also require the use of an agent for improving the adhesion.
An aim of the present invention is to provide novel single-component organopolysiloxane compositions which are obtained by starting directly from organopolysiloxane polymers comprising hydroxyl groups in their structures.
Another aim of the present invention is to provide single-component organopolysiloxane compositions of this type which will undergo in situ, during their preparation, a reaction for complete functionalization or functionalization which is as close as possible to the maximum degree of functionalization accessible and will exhibit, for this reason, a high level of stability on storage in cartons.
Yet another aim of the present invention is to provide single-component organopolysiloxane compositions which do not necessarily resort to the use of an agent for improving the adhesion and which make it possible to obtain, without use of such an agent, translucent elastomers with very good adhesion to various substrates, in particular plastics, such as, for example, poly(vinyl chloride) (PVC) and poly(methyl methacrylate) (PMMA).
Yet another aim of the present invention is to provide single-component organopolysiloxane compositions which can be prepared by using, without distinction, a batchwise mode or a continuous mode.
The discovery has thus been made, and it is this which forms the subject-matter of the present invention, of single-component organopolysiloxane compositions which are stable on storage in the absence of moisture and which crosslink to translucent and adherent elastomers in the presence of moisture, characterized in that they are capable of being obtained by carrying out, in a single closed reactor with stirring, operating according to a batchwise mode or a continuous mode, successive stages 1 to 3 defined below:
stage 1: functionalization stage, during which:
(i) at least one reactive linear diorganopolysiloxane A comprising a hydroxyl group at each chain end, of formula: 
in which:
the R1 substituents, which are identical or different, each represent an aliphatic, or aromatic, saturated or unsaturated, substituted or unsubstituted, C1 to C13 monovalent hydrocarbonaceous radical;
n has a value sufficient to confer, on the diorganopolysiloxanes of formula (I), a dynamic viscosity at 25xc2x0 C. ranging from 1 000 to 1 300 000 mPaxc2x7s;
(2i) and at least one hydroxylated organopolysiloxane resin B exhibiting, in its structure, at least two different units chosen from those of formulae (Rxe2x88x92)3SiO1/2 (M unit), (R1)2SiO2/2 (D unit), R1SiO3/2 (T unit) and SiO2 (Q unit), at least one of these units being a T or Q unit and the R1 radicals, which are identical or different, having the meanings given above with respect to the formula (I), the said resin having a content by weight of hydroxyl group ranging from 0.1 to 10%;
(3i) are reacted with at least one polyalkoxysilane C of formula:
(R2)aSi[(OCH2CH2)bOR3]4xe2x88x92axe2x80x83xe2x80x83(II)
in which:
the R2 substituent represents an aliphatic, cyclanic or aromatic, saturated or unsaturated, substituted or unsubstituted, C1 to C13 monovalent hydrocarbonaceous radical;
the R3 symbols, which are identical or different, each represent a linear or branched C1 to C8 alkyl radical;
a is zero or 1;
b represents zero or 1;
(4i) the reaction of (i) and (2i) with (3i) being carried out in the presence of a catalytically effective amount of a functionalization catalyst D, with the exception of the use of an organic titanium derivative;
(5i) it being possible for the reaction medium of stage 1 additionally to comprise;
at least one aliphatic C1 to C3 alcohol xcex5; and/or
at least one nonreactive linear diorganopolysiloxane F of formula: 
in which:
the R1 substituents, which are identical or different, have the same meanings as those given above for the reactive diorganopolysiloxane A of formula (I);
m has a value sufficient to confer, on the polymers of formula (III), a dynamic viscosity at 25xc2x0 C. ranging from 10 to 200 000 mPaxc2x7s;
stage 2: blending (or compounding) stage, during which:
(6i) an inorganic filler G based on amorphous silica in the form of a solid;
(7i) an effective amount of a curing catalyst H comprising at least one organic titanium derivative chosen from the group consisting of:
H1 monomers of formula:
Ti[(OCH2CH2)cOR4]4xe2x80x83xe2x80x83(IV)
in which:
the R4 substituents, which are identical or different, each represent a linear or branched C1 to C12 alkyl radical;
c represents zero, 1 or 2;
with the conditions according to which, when the c symbol represents zero, the R4 alkyl radical has from 2 to 12 carbon atoms and, when the c symbol represents 1 or 2, the R4 alkyl radical has from 1 to 4 carbon atoms;
H2 polymers resulting from the partial hydrolysis of the monomers of formula (IV) in which the R4 symbol has the abovementioned meaning with the c symbol representing zero;
(8i) optionally at least one nonreactive linear diorganopolysiloxane F corresponding to the formula (III) mentioned above; and
(9i) optionally at least one auxiliary agent I known to a person skilled in the art, which is generally chosen, when it is needed, according to the applications in which the compositions according to the present invention are employed;
are introduced in any order into the functionalization medium of stage 1, which is kept stirred;
stage 3: finishing stage, during which the base blend obtained, kept stirred, is subjected to a devolatilization operation carried out under a pressure below atmospheric pressure.
In accordance with a preferred arrangement of the invention, the following are used to prepare the single-component organopolysiloxane compositions, on the basis of 100 parts by weight of hydroxylated linear diorganopolysiloxane(s) A:
from 3 to 30 parts of hydroxlyated resin(s) B,
from 2 to 15 parts of polyalkoxysilane(s) C,
a catalytically effective amount of functionalization catalyst D,
from 0 to 2 parts of alcohol(s) E,
from 0 to 30 parts of nonreactive linear diorganopolysiloxane(s) F,
from 2 to 40 parts of siliceous filler G,
from 0.3 to 5 parts of organic titanium derivative(s) H, and
from 0 to 20 parts of auxiliary agent(s) I.
In accordance with a more preferred arrangement of the invention, the following are used to prepare the single-component organopolysiloxane compositions, on the basis of 100 parts by weight of hydroxylated linear diorganopolysiloxane(s) A:
from 5 to 15 parts of hydroxlyated resin(s) B,
from 3.5 to 7 parts of polyalkoxysilane(s) C,
a catalytically effective amount of functionalization catalyst D,
from 0 to 1 part of alcohols(s) E,
from 5 to 20 parts of nonreactive linear diorganopolysiloxane(s) F,
from 8 to 20 parts of siliceous filler G,
from 0.5 to 3 parts of organic titanium derivatives(s) H, and
from 0 to 20 parts of auxiliary agent(s) I.
The R1 substituents mentioned above for the organopolysiloxane polymers A and F (optional) comprise:
alkyl and haloalkyl radicals having from 1 to 13 carbon atoms, such as the methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, 2-ethylhexyl, octyl, decyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl or 4,4,4,3,3-pentafluorobutyl radicals,
cycloalkyl and halocycloalkyl radicals having from 5 to 13 carbon atoms, such as the cyclopentyl, cyclohexyl, methylcyclohexyl, propylcyclohexyl, 2,3-difluorocyclobutyl or 3,4-difluoro-5-methyl-cycloheptyl radicals,
alkenyl radicals having from 2 to 8 carbon atoms, such as the vinyl, allyl or 2-butenyl radicals,
mononuclear aryl and haloaryl radicals having from 6 to 13 carbon atoms, such as the phenyl, tolyl, xylyl, chlorophenyl, dichlorophenyl or trichlorophenyl radicals,
cyanoalkyl radicals in which the alkyl linkages have from 2 to 3 carbon atoms, such as the xcex2-cyanoethyl and xcex3-cyanopropyl radicals.
Mention may be made, as concrete examples of (R1)2SiO2/2 or (R1)2SiO units present in the hydroxylated diorganopolysiloxanes A of formula (I) and in the optional nonreactive diorganopolysiloxanes F of formula (III), of:
(CH3)2SiO,
CH3(CH2xe2x95x90CH)SiO,
CH3(C6H5)SiO,
(C6H5)2SiO,
CF3CH2CH2(CH3)SiO,
NCxe2x80x94CH2CH2(CH3)SiO,
NCxe2x80x94CH(CH3)CH2(CH2xe2x95x90CH)SiO,
NCxe2x80x94CH2CH2CH2(C6H5)SiO.
It must be understood that, in the context of the present invention, use may be made, as hydroxilated polymers A of formula (I), of a blend composed of several hydroxylated polymers which differ from one another in the value of the viscosity and/or the nature of the substituents bonded to the silicon atoms. It must furthermore be pointed out that the hydroxylated polymers A of formula (I) can optionally comprise T units of formula R1SiO3/2 and/or SiO2 units in the proportion of at most 1% (these % values expressing the number of T and/or Q units per 100 silicon atoms). The same comments apply to the (optional) nonreactive polymers F of formula (III).
The R1 substituents of the hydroxylated polymers A and of the (optional) nonreactive polymers F advantageously used, because of their availability in industrial products, are the methyl, ethyl, propyl, isopropyl, n-hexyl, phenyl, vinyl and 3,3,3-trifluoro-propyl radicals. More advantageously, at least 80% by number of these substituents are methyl radicals.
Use is made of hydroxylated polymers A having a dynamic viscosity at 25xc2x0 C. ranging from 1 000 to 1 000 000 mPaxc2x7s and preferably ranging from 10 000 to 200 000 mPaxc2x7s.
As regards the (optional) nonreactive polymers F, they exhibit a dynamic viscosity at 25xc2x0 C. ranging from 10 to 200 000 mPaxc2x7s and preferably ranging from 50 to 150 000 mPaxc2x7s.
The nonreactive polymers F, when they are used, can be introduced either entirely in the reaction medium of stage 1 or entirely in the reaction medium of stage 2 or simultaneously in both these media; in the latter case, the fraction of constituent F introduced in the medium of stage 1 may be identical to or different from (in terms of nature and/or of proportions of the constituent in each fraction) the fraction of constituent F also introduced in the medium of stage 2. Preferably, the constituent F is introduced entirely in the reaction medium of stage 1.
Mention may be made, as examples of R1 substituents of the hydroxylated organopolysiloxane resins B which are suitable or which are advantageously used, of the various R1 radicals of this type particularly mentioned above for the hydroxylated polymers A and the (optional) nonreactive polymers F. These silicone resins are well known branched organopolysiloxane polymers, the processes for the preparation of which are disclosed in numerous patents. Mention may be made, as concrete examples of resins which can be used, of the MQ, MDQ, TD and MDT resins.
Mention may preferably be made, as examples of resins which can be used, of the hydroxylated organopolysiloxane resins B not comprising a Q unit in their structures. Mention may more preferably be made, as examples of resins which can be used, of the hydroxylated TD and MDT resins comprising at least 20% by weight of T units and having a content by weight of hydroxyl group ranging from 0.3 to 5%. Even more preferably, use is made of resins of this type in the structures of which at least 80% by number of the R1 substituents are methyl radicals. The hydroxyl groups of the B resins can be carried by the M, D and/or T units.
As regards the polyalkoxysilanes C of formula (II), mention may be made, as concrete examples of R2 substituents which are suitable or which are advantageously used, of the same radicals as those particularly mentioned above for the R1 substituents of the hydroxylated polymers A and of the nonreactive polymers F. Mention may be made, as examples of R3 radicals, of C1 to C4 alkyl radicals, such as the methyl, ethyl, propyl, isopropyl and n-butyl radicals.
Mention may in particular be made, among the polyalkoxysilanes C of formula (III) which are used in the context of the present invention, of those listed below:
Si(OCH3)4
Si(OCH2CH3)4
Si(OCH2CH2CH3)4
(CH3O)3SiCH3
(C2H5O)3SiCH3
(CH3O)3Si(CHxe2x95x90CH2)
(C2H5O)3Si(CHxe2x95x90CH2)
(CH3O)3Si(CH2xe2x80x94CHxe2x95x90CH2)
(CH3O)3Si[CH2xe2x80x94(CH3)Cxe2x95x90CH2]
(C2H5O)3Si(OCH3)
Si(OCH2xe2x80x94CH2xe2x80x94OCH3)4
CH3Si(OCH2xe2x80x94CH2xe2x80x94OCH3)3
(CH2xe2x95x90CH)Si(OCH2CH2OCH3)3
C6H5Si(OCH3)3
C6H5Si(OCH2xe2x80x94CH2xe2x80x94OCH3)3.
The polyalkoxysilanes C of formula (III) preferably used are: Si(OC2H5)4, CH3Si(OCH3)3, CH3Si(OC2H5)3, (C2H5O)3Si(OCH3), (CH2xe2x95x90CH)Si(OCH3)3 and (CH2xe2x95x90CH)Si(OC2H5)3.
As regards the functionalization catalyst D, in the presence of which the reaction of the hydroxylated polymers A and of the hydroxylated resins B with the polyalkoxysilanes C takes place, recourse may be had in particular to the following compounds:
potassium acetate (cf. U.S. Pat. No. 3,504,051),
various inorganic oxides (cf. FR-A-1 495 011),
carbamates (cf. EP-A-0 210 402),
lithium hydroxide (cf. EP-A-0 367 696),
sodium hydroxide or potassium hydroxide (cf. EP-A-0 457 693).
In the context of the present invention, the use is recommended, as catalyst D, of lithium hydroxide of formula LiOH or LiOH.H2O. It is preferably used in solution in at least one aliphatic alcohol E having from 1 to 3 carbon atoms, such as, for example, methanol, ethanol, isopropanol or a mixture of these alcohols. When one (or several) alcohol(s) is(are) present in the reaction medium, the amount employed lies within the range from 0.1 to 2 parts by weight and preferably from 0.2 to 1 cart by weight per 100 parts of hydroxylated polymer(s) A.
The term xe2x80x9ccatalytically effective amount of catalyst Dxe2x80x9d is understood to mean an amount such that the functionalization reaction rate is as high as possible, in particular on using Si(OC2H5)4, CH3Si(OCH3)3, CH3Si(OC2H5)3, (C2H5O)3Si(OCH3), (CH2xe2x95x90CH)Si(OCH3)3 and (CH2xe2x95x90CH)Si(OC2H5)3 as functionalization agent. In the majority of cases, use is made of 0.01 to 5 mol of catalyst per 1 mol of silanol groups (xe2x89xa1Sixe2x80x94OH) contributed, first, by the hydroxylated polymer(s) A and, secondly, the hydroxylated resin(s) B. In the preferred case, in which lithium hydroxide is resorted to, use is made of 0.005 to 0.5 mol of LiOH per 1 mol of silanol groups.
As indicated above, the inorganic filler G is composed of amorphous silica in the form of a solid. The physical state in which the silica is provided is immaterial, that is to say that the said filler can be provided in the form of a powder, micropearls, granules or beads, provided that this filler is sufficiently dispersed within the compositions according to the present invention to achieve the desired objective of translucency.
Any precipitated silica or pyrogenic silica (or fumed silica) known to a person skilled in the art is suitable as amorphous silica capable of being employed in the invention. Of course, composites of different silicas can also be used.
Preference is given to precipitated silicas in the powder form, fumed silicas in the powder form, or their mixtures; their BET specific surface area is generally greater than 40 m2/g and preferably between 100 and 300 m2/g; use is more preferably made of fumed silicas in the powder form.
These fillers may have been surface-modified by treatment with the various organosilicon compounds customarily employed for this use. Thus, these organosilicon compounds can be organochlorosilanes, diorganocyclopolysiloxanes, hexaorganodisiloxanes or hexaorganodisilazanes (cf. FR-A-1 126 884, FR-A-1 136 885 and FR-A-1 236 005). The treated fillers include, in the majority of cases, from 2 to 20% of their weight of organosilicon compounds.
As regards the curing catalyst H, mention may be made, as examples of R4 symbols in the organic titanium derivatives Hi of formula (IV), of the radicals: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, 2-ethylhexyl, octyl, decyl and dodecyl.
Mention may be made, as concrete examples of H1 monomers of formula (IV), of: ethyl titanate, propyl titanate, isopropyl titanate, butyl titanate, 2-ethyl-hexyl titanate, octyl titanate, decyl titanate, dodecyl titanate, xcex2-methoxyethyl titanate, xcex2-ethoxyethyl titanate, xcex2-propoxyethyl titanate or the titanate of formula Ti[(OCH2CH2)2OCH3]4. Mention may be made, as concrete examples of H2 polymers originally from the partial hydrolysis of titanate monomers, of: the H2 polymers originating from the partial hydrolysis of isopropyl, butyl or 2-ethylhexyl titanates.
In carrying out the invention, use is preferably made, as curing catalyst, of the following H1 monomer titanates, taken alone or as a mixture: ethyl titanate, propyl titanate, isopropyl titanate or butyl (n-butyl) titanate.
The single-component organopolysiloxane compositions according to the present invention can additionally comprise one or more auxiliary agent(s) I such as in particular, per 100 parts by weight of hydroxylated linear diorganopolysiloxane polymer(s) A:
optionally from 0.1 to 10 parts of an adhesion promoter I1,
optionally an effective amount of at least one compound taken from the group formed by antifungals I2, bactericides I3, inert organic diluents I4 (such as, for example: toluene, xylene, heptane, white spirit, trichloroethylene or tetrachloroethylene), plasticizers I5 belonging, for example, to the group of the alkylbenzenes with a molecular weight of greater than 200 g/mol comprising a branched or unbranched alkyl residue having from 10 to 30 carbon atoms, and thixotropic agents I6.
The adhesion promoter I1, when one of them is used, is preferably chosen from organosilicon compounds carrying both (1) hydrolysable groups bonded to the silicon atom and (2) organic groups substituted by the radicals chosen from the group of the isocyanato, epoxy, alkenyl and isocyanurate radicals.
Mention may be made, as illustration, of the organosilicon compounds corresponding to the formulae below (accompanied by the numbers of the patents in which they are disclosed): 
The single-component organopolysiloxane compositions in accordance with the present invention are prepared with moisture excluded by carrying out the preparation in a closed reactor, equipped with a stirrer, in which, if need be, a vacuum can be applied and then the air driven of can optionally be replaced by an anhydrous inert gas, for example by nitrogen.
For this preparation, it is recommended to use an installation, operating according to a batchwise mode or a continuous mode, which makes it possible:
to intimately stir, with moisture excluded: in stage 1, the constituents A, B, C, D, E (optional) and F (optional); then, in stage 2, the reaction mixture from stage 1 made up by the addition of the constituents G, H, F (optional) and I (optional); and
to discharge, in stage 3, the volatile materials present (low molecular weight polymers, alcohol formed during the functionalization reaction, alcohol E optionally used).
Mention may be made, as examples of installations, of: slow dispersers, paddle, propeller, arm or anchor mixers, planetary mixers, hook mixers, or single-screw or multiple-screw extruders.
Each of the stages employed in this preparation is carried out at a temperature lying within the range from 10 to 110xc2x0 C. Preferably, each of the stages is carried out at a temperature ranging from 15 to 90xc2x0 C.
Stage 1 is carried out for a sufficient period of time (ranging, for example, from 10 seconds to 10 minutes) to carry out a reaction for complete functionalization or functionalization which is as close as possible to the maximum degree of functionalization accessible under the operating conditions chosen.
Stage 2 is carried out for a sufficient period of time (ranging, for example, from 10 seconds to 30 minutes) to arrive at homogeneous compositions.
Stage 3 is generally carried out under a reduced pressure of between 20xc3x97102 Pa and 900xc3x97102 Pa for a sufficient period of time (ranging, for example, from 10 seconds to 1 hour) to discharge all the volatile materials.
The compositions in accordance with the invention are stable on storage in the absence of water, curing from ambient temperature in the presence of moisture. The curing (or the crosslinking) takes place from the exterior toward the interior of the body of the compositions. First a surface skin is formed and then the crosslinking continues into the body.
They can be employed in multiple applications, such as pointing in the construction industry, or the assembling and adhesive bonding of the most diverse materials (metals; plastics, such as, for example, PVC or PMMA; natural and synthetic rubbers; wood; board; earthenware; brick; glass; stone; concrete; masonry components), both in the context of the construction industry and in that of the automobile, domestic electrical appliance and electronics industries.
The compositions in accordance with the invention result, after curing, in translucent elastomers which have very good adhesion to various substrates and which furthermore exhibit the advantage, first, of not yellowing over time under the oxidizing action of the air and, secondly, of not being corrosive with respect to metals or metal alloys, such as, for example, aluminum, steel, copper or bronze, with which they are in contact or to which they adhere.